TW200806816A - Crystalline chromium deposit - Google Patents

Abstract

A crystalline chromium deposit having a lattice parameter of 2.8895 +/- 0.0025 Å, and an article including the crystalline chromium deposit. An article including a crystalline chromium deposit, wherein the crystalline chromium deposit has a {111} preferred orientation. A process for electrodepositing a crystalline chromium deposit on a substrate, including providing an electroplating bath comprising trivalent chromium and a source of divalent sulfur, and substantially free of hexavalent chromium; immersing a substrate in the electroplating bath; and applying an electrical current to deposit a crystalline chromium deposit on the substrate, wherein the chromium deposit is crystalline as deposited.

Description

200806816 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for electrodepositing crystalline chromium from a trivalent chromium bath deposition, electrodepositing the chromium deposits, and having such a coating thereon Objects of chromium deposits. [Prior Art] Chromium plating began in the early 20th century or in the late 19th century and provided an excellent functional surface coating in both wear resistance and corrosion resistance. However, in the past, this excellent coating was obtained as a functional coating (unlike decorative coatings) only from hexavalent chromium plating baths. The chromium deposited from the hexavalent chromium bath is deposited in crystalline form, which is highly desirable. Amorphous chrome plates are useless. The chemicals used in the art are mainly hexavalent chromium ions which are considered to be carcinogenic and toxic. The hexavalent chromium plating operation has strict and several environmental restrictions. Although several methods have been developed in the industry to reduce hexavalent chromium to reduce hazards, both industrial and academic have spent several years looking for suitable alternatives. Considering the importance and advantages of chrome ore deposits, the most obvious alternative source for chromium plating is trivalent chromium. Trivalent chromium salts are less harmful to health and the environment than hexavalent chromium compounds. Several different trivalent chromium electrodeposition baths have been tested and tested over several years. However, none of these trivalent chromium baths have successfully produced chromium deposits that are as reliable as those obtained from the hexavalent chromium electrodeposition process. Hexavalent chromium is extremely toxic and is subject to regulations not controlled by trivalent chromium. The latest OSHA guidelines for hexavalent chromium exposure are published on 79/0, 79/5,

Occupational Exposure to Hexavalent Chromium; Final h/e. In this Code, the alternative is described as an “ideal (engineering) control 119773.doc 200806816 measure” and “should always consider replacing a toxic material with a lesser dangerous alternative^ (Federal Register/VoL 719 No. S9/Tuesday, February 28, like, p. 10345). Therefore, the industry is based on the use of another form of chromium instead of hexavalent chromium based on strong government orders. However, up to the present invention, none of the methods successfully electrodeposited a reliable and consistent crystalline chromium deposit from a trivalent or other non-hexavalent chromium plating bath. In general, in the prior art, all trivalent chromium electrodeposition processes formed amorphous chromium deposits. Although the amorphous chromium deposit can be annealed at about 35 0-3 70 C and thereby produce a crystalline chromium deposit, the annealing results in the formation of undesirable large cracks, which renders the chromium deposit substantially useless. . A large crack is defined as a crack that extends through the entire thickness of the chrome layer up to the substrate. Since the large cracks reach the substrate, the surrounding material is brought into contact with the substrate, so the chromium deposit cannot provide its corrosion resistance. It is believed that these large cracks originate from the crystallization process because the desired body-centered cubic crystal form has a smaller volume than the deposited amorphous chromium deposit and the resulting stress causes the chromium deposit to rupture, forming large cracks. In contrast, crystalline chromium deposits from hexavalent electrodeposition methods typically contain small cracks that extend only a portion of the distance from the surface of the deposit to the substrate and do not extend across the entire thickness of the chromium deposit. This is where some of the crack-free chromium deposits from hexavalent chromium electrolytes are available. The frequency of occurrence of small cracks (if present) in chromium from hexavalent chromium electrolytes is about 4 每 or more cracks per cm, and is cracked in amorphous deposits from a mussel chrome electrolyte that has been annealed to form crystalline chromium. The number of times (right exists) is less than about an order of magnitude. Even with a lower frequency, these large cracks cause trivalent chromium-derived crystalline deposits to be used for functioning. 119773.doc 200806816 is not accepted. Functional chromium deposits need to provide wear and corrosion resistance, and the presence of large cracks makes the article susceptible to corrosion, and thus the chromium deposits are unacceptable. The bismuth chromium electrodeposition method can successfully deposit a decorative chromium deposit. However, clothing chrome is not a functional chrome and does not provide the benefits of functional chrome.

Although it seems that applying decorative I deposits and making them suitable for functional, sedimentary systems is a simple matter, but this has not been achieved. On the contrary, despite the fact that people have been working hard to solve this problem and achieve the goal of divalent chromium electrodeposition methods that can form crystalline collateral deposits, they still fail to achieve the above objective 0. It is based on the method of trivalent chromium that it takes about half of the electricity required by the hexavalent method. Using Faraday's law, and assuming a chromium density of 7.14 g/cm 3, for a hexavalent chromium plating process, the 2% cathodic efficiency process has a rate of mineralization t (where the applied current density is 50) A/dm^ 56 6 μm/dm 2 /hr. Using the same cathode efficiency and current density, the chromium deposit from the trivalent state has twice the thickness in the same period. For all of these reasons, the long-term

At the barren industry, there is still a need for a functional deposition of crystallization of collateral deposits, thunder and sedimentation, U accumulation of primary enthalpy, cold accumulation and enthalpy formation of this chrome deposit and the use of this chrome deposit得, ^ clothing in the 々 object, wherein the chrome deposit has no large 4 lines and can provide functional equivalent to the functional hard path, / pediatric product obtained from the hexavalent chrome Abrasion resistance and corrosion resistance ap Prior to this, the industry has not been able to meet the urgent need for a bath and method that can freely fluorinate 169773.doc 200806816 for crystallization of functional chromium deposits. The invention provides a chromium deposit which is deposited as a tantalum chromium solution upon deposition. While the present invention can be used to form decorative chromium deposits, it is primarily concerned with functional chromium deposits, and in particular for functional crystalline chromium deposits previously available only by means of hexavalent electrodeposition processes. The present invention provides a solution to the problem of providing crystalline functional chromium deposits from a trivalent chromium bath substantially free of hexavalent chromium, but which is still capable of providing substantially the same as those obtained from the six-electrode electrodeposition A product with equivalent functional characteristics. The present invention provides a solution to the problem of replacing a hexavalent chromium plating bath. [Embodiment] As used herein, a decorative chromium deposit is typically applied to an electrodeposition recording or nickel & to a coating, or to a tantalum steel and a nickel or nickel alloy coating (the combined thickness of which does not exceed 3 microns) A chromium deposit having a thickness less than 丨 microns and typically less than 〇 8 microns. As used herein, a functional chromium deposit is a chromium deposit applied (usually directly) to a substrate (eg, strip steel ECCS (electrolyzed chromium coated steel, where the chromium thickness is typically greater than ❹ or 丨 micron) and is For industrial rather than decorative applications, chromium deposits are typically applied directly to the substrate. Industrial coatings utilize the specific properties of chromium, including its hardness, its resistance to heat, abrasion, corrosion, and surnames. And its low coefficient of friction. Even if it has nothing to do with performance, many users still hope that the functional chromium deposits have the appearance of H9773.doc 200806816. The thickness of functional chromium deposits can be between the above. 8 or 1 micron to 3 microns or more. In some cases, a functional chromium deposit is applied to a ''impact plate such as nickel or iron on a substrate) or a "dual" system in which nickel, Iron or alloy coatings have a thickness greater than 3 microns and chromium thickness typically exceeds 3 microns. Functional chrome plating and deposits are commonly referred to as "hard" chrome and deposits. Decorative chrome plating baths are involved in a wide plating range. thin Chromium deposits so

Where the king covers an irregular shape of the object. Functional chrome plating, on the other hand, is designed for thicker deposits on regularly shaped articles where plating at higher current efficiencies and higher current densities is extremely important. Previous chrome plating methods using trivalent chromium ions have generally been applied to form only "decorative" retouching. The present invention provides "hard" or functional chromium deposits, but is not limited thereto and can be used for decorative chrome finishes. "Hard" or "Functional" "Decorative" Chromium Sediment is a well-known term for this technology. As used herein, when reference (for example, the use of an electric ore bath or other composition, "substantially free of hexavalent chromium" refers to the electromineral bath or other composition so described, η 4, 5 added Hexavalent chromium. It should be understood that this bath or other combination of coarse slag marks "valence chrome" which is used as a by-product of the addition of the bath or composition to the electrolysis or chemical process. == The term "better orientation" has the familiarity with crystallographic techniques to align with a particular direction <heart], while the enthalpy exhibits a tendency to drought in the host material. Therefore, the preferred orientation can be 119773.doc 200806816 Such as M100丨, U10}, {ill} and its integral multiple (eg (222)). The present invention provides a reliable and consistent body-centered cubic (BCC) crystalline chromium deposit from a trivalent chromium bath, the bath Substantially free of hexavalent chromium, and wherein the chromium deposit is deposited in a crystalline state, and the helmet; 隹lf. ^ and ..., and further processed to crystallize the chromium deposit. Therefore, the present invention has not been solved for a long time. Reliable and consistent crystallization from electroplating baths and methods that are essentially free of hexavalent chromium The problem of chromium deposits provides a solution.

The crystalline chromium deposit of the present invention in the shell example was tested to be substantially free of large cracks using standard test methods. In other words, in this embodiment, under the standard test method, substantially no large crack was observed when the sample of the deposited chromium was detected. In one embodiment, the crystalline chromium deposit of the present invention has a cubic lattice parameter of 2.8895 + plant 0.0025 angstroms (person). It should be noted that the term "lattice parameters, and sometimes also as ''lattice constants'. For the purposes of the present invention, these terms are considered synonymous. It should be noted that for body-centered cubic chromium, The unit cell is a cube, so there is a single lattice parameter. It is more appropriate to refer to this lattice parameter as a cubic lattice parameter, but in this paper it is simply referred to as "lattice parameter,". In one embodiment, the crystalline chromium deposit of the present invention has a lattice parameter of 2.8895 angstroms + 〇〇〇 2 〇. In another embodiment, the crystalline chromium deposit of the present invention has a lattice parameter of 2.8895 angstroms + / _0 0015 angstroms. In still another embodiment, the crystalline chromium deposit of the present invention has a lattice parameter of 2.8895 Å + / _ 〇 〇〇 1 〇. Some specific examples herein provide crystalline deposits having lattice parameters within the ranges. The pyrometallurgical elemental crystalline chromium has a lattice parameter of 2.8839 angstroms. 119773.doc -11- 200806816 Crystalline chromium deposited from a hexavalent chromium bath has a lattice parameter from about 2.88 〇 9 Å to about 2.8858 angstroms. The annealed electrodeposited trivalent deposited amorphous chromium has a lattice parameter from about 2.88 ΐ 8 Å to about 2.8852 angstroms, but also has large cracks. The lattice parameter of the chromium deposit of the present invention is greater than that of other conventional crystalline chromium forms. While not wishing to be bound by theory, it is believed that this difference may be due to the inclusion of heteroatoms (e.g., sulfur, nitrogen, carbon, oxygen, and/or hydrogen) in the crystal lattice of the crystalline chromium deposit obtained in accordance with the present invention. In one embodiment, the crystalline chromium deposit of the present invention has a preferred orientation of {111. In one embodiment, the crystalline chromium deposit is substantially free of large cracks. In a single embodiment, g crystallizes the collateral deposit up to about 3 〇 〇. No large cracks were formed at the temperature of the crucible. In one embodiment, when the crystalline chromium deposit is heated to a temperature of up to about 3 Torr (TC), its crystal structure does not change. In one embodiment, the crystalline chromium deposit further includes carbon, nitrogen, and sulfur. In the chromium deposit, in one embodiment, the crystalline chromium deposit comprises from about 1% by weight to about 1% by weight of sulfur. In another embodiment, the chromium deposit comprises about 15% by weight. Up to about 6 weights of lanthanum/lanthanum sulfur. In another embodiment, the chromium deposit comprises from about 1.7% to about 4% by weight sulfur. The sulfur is present in the deposit as elemental sulfur and may be crystalline a portion of the grid, ie, instead of and thus occupying a position of the chromium atom in the lattice or occupying a position in the tetrahedral or octahedral pore location and distorting the lattice. In one embodiment, the source of sulfur may be Divalent sulfur compounds. Further details regarding exemplary sulfur sources are provided below. H9773.doc -12- 200806816 In one embodiment, the deposit comprises selenium and/or germanium in place of sulfur or, in addition to sulfur Also includes enamel and/or hoof. It should be noted that since the hexavalent chromium bath Some forms of crystalline chromium comprise sulfur 'but the chromium content of the chromium deposits is substantially lower than the sulfur content of the crystalline chromium deposit of the present invention. In one embodiment, the crystalline chromium deposit comprises about 0.1% by weight. Up to about 5% by weight of nitrogen. In another embodiment, the crystalline chromium deposit comprises from about 0.5% by weight to about 3% by weight of nitrogen. In another embodiment, the crystalline chromium deposit contains About 4% by weight of nitrogen. In one embodiment, the crystalline chromium deposit comprises from about 1% by weight to about 5% by weight carbon. In another embodiment, the crystalline chromium deposit comprises about 0.5%. % by weight to about 3% by weight of carbon. In another embodiment, the crystalline chromium deposit comprises about 1/4% by weight of carbon. In one embodiment, the crystalline chromium deposit comprises less than the amount causing the chromium deposit The material becomes an amorphous quantity of carbon. In other words, above a certain content, in one embodiment is greater than about 10% by weight, the carbon causes the chromium deposit to become amorphous, and thus is from the scope of the invention Excluded. Therefore 'the carbon content should be controlled so as not to sink the chrome The deposit becomes amorphous. The carbon may exist as elemental carbon or as carbide carbon. If the carbon system exists as 70, it may exist as graphite or as amorphous carbon. In one embodiment, the crystalline chromium deposit It comprises from about 1.7% by weight to about 4% by weight of sulfur, from about 0% by weight to about 5% by weight of nitrogen, and from about 1% by weight to about 10% by weight of carbon. The crystalline chromium deposit of the present invention is derived from trivalent chromium. Electroplating bath electrodeposition. The three 4 shell chromium/gluten babe does not contain hexavalent chromium. In one embodiment, the bath does not contain hexavalent chromium which can be measured by 119773.doc -13-200806816. Provided as: chromium chloride CrCl3, chromium fluoride CrF3, chromium nitrate Cr(N03)3, chromium oxide Cr203, scale Smann chromium CrP04, or a commercially available solution, for example from, for example, McGean Chemical Company or Sentury Reagents of chromium dichloride, chromium carbonate solution or chromium sulfate solution. Trivalent chromium is also used as chromium sulphate/sodium sulphate or potassium sulphate, such as Cr(0H)S04.Na2S04, commonly known as chrome tantalum (chrometan or kromsan), which is commonly used in leather tanning chemicals. Purchased from companies such as Elementis, Lancashire Chemical, and Soda Sanayii. As described below, the trivalent chromium can also be provided as a sulphuric acid Cr (HCOO) 3 from Sentury Reagents. The concentration of the trivalent chromium may range from about 〇1 mole (M) to about 5 。. The higher the concentration of trivalent chromium, the higher the current density that can be applied without causing dendritic deposits, and thus the faster the crystallization chromium deposition rate that can be achieved. The trivalent chromium bath may further comprise an organic additive such as formic acid or a salt thereof such as one or more of sodium formate, potassium citrate, ammonium formate, calcium citrate, magnesium formate, and the like. Other organic additives including amino acids (e.g., glycine) and thiocyanate may also be used to prepare crystalline chromium deposits from trivalent chromium and their use is within the scope of one embodiment of the invention. Chromium ruthenate (ΠΙ) (i.e., Cr(HCOO)3) can also be used as a source of both trivalent chromium and formic acid. The trivalent chromium bath may further comprise a source of nitrogen which may be in the form of ammonium hydroxide or a salt thereof or may be a primary, secondary or tertiary alkylamine wherein the alkyl group is a C!-C6 alkyl group. In one embodiment, the nitrogen source is not a quaternary ammonium compound. In addition to the amine, an amino acid, a hydroxylamine (e.g., quadrol), and a polyhydric hydroxy alkanolamine can be used as the nitrogen source. In one embodiment of such nitrogen sources, 119773.doc -14- 200806816

It is added as a salt (for example, an amine salt such as a hydrogen salt).

As described above, the crystalline chromium is attached to 'π aa』, , for example, the hydrogen contained in the bath, and the other groups may be derived from the group or may be derived from formic acid or a salt thereof, or Otherwise, the crystalline chromium may comprise oxygen and hydrogen, a portion obtained (including electrolysis of water), or a dog bath component. In addition to chromium atoms, the crystalline chromium deposit can co-deposit other metals. As will be appreciated by those skilled in the art, such metals may be suitable for addition to the three-shell chromium plating bath (if desired) to obtain various crystalline alloys of chromium in the deposit. Such metals include, but are not necessarily limited to, Re, Cu, Fe, w, Ni, Μη, and may also include (for example, (phosphorus). In fact, in this method, it may be fused from an aqueous solution directly or by, for example, 1 > ]: 1^}^ or Brenner, inducing all elements of electrodeposition. In one embodiment, the alloy metal is not aluminum. As is known in the art, metals that can be electrodeposited from aqueous solutions include: Ag, As, Au ' Bi, Cd, c〇, Cr, Cu, I, &, &, &, Mn, Mo, Ni, p, pb, pd, pt, Rh, &, Ru, s, Exo, ~, Sn, Te, Ti, w&Zn, and inducible elements include B, c, and N. As will be appreciated by those skilled in the art, the co-deposited metal or atomic system is in the deposit. The amount of chromium is present, and as in the absence of the co-deposited M. genus or atom, the resulting crystalline chromium deposit, the resulting > redundancy should be body-centered cubic crystal. The divalent chromium bath Further having a pH of at least 4 〇, and the pH can be as high as about 6.5. In one embodiment, the pH of the trivalent chromium bath is from about 4.5 to about H9773.doc • 15- 200806816 6·5 'and in another embodiment, the pH of the trivalent chromium bath is from about 4.5 to about 6 ' and in another embodiment, the pH of the trivalent chromium bath is from about 5 to about 6 Between and in one embodiment, the pH of the trivalent chromium bath is about 5.5. In one embodiment, the trivalent chromium bath is maintained at about 35 during the process of electrodepositing the crystalline chromium deposit of the present invention. 〇 to a temperature between about 115. or the lower of the boiling point of the solution. During the process of electrodepositing the crystalline chromium deposit, 'in one embodiment, the bath temperature is from about 45 ° C to About 75 ° C, and in another embodiment, the bath temperature is from about 50 ° C to about 65 ° C, and in one embodiment, the bath temperature is maintained at about 55 ° C. During the process of inventing the crystalline chromium deposit, the current is applied at a current density of at least about 10 amps and 7 square decimeters (A/dm2). During the electrodeposition of the crystalline chromium deposit from the trivalent chromium bath in accordance with the present invention, In another embodiment, the current density is from about 1 A/dm2 to about 200 A/dm2, and in another embodiment, the current density is from about 1 A/dm2. About 100 A/dm' and in another embodiment, the current density is from about 2 A/dm2 to about 70 A/dm2, and in yet another embodiment, the current density is from about 3 A/A. Dm2 to about 60 A/dm 2. During the process of electrodepositing the crystalline chromium deposit of the present invention, the current may be applied using any one of a direct current, a pulsating waveform, or a pulsating periodic inverse waveform, or any combination of two or more thereof. Therefore, in an embodiment, the present invention provides a method for electrodepositing a crystalline chromium deposit on a substrate, comprising the steps of: providing a water-based electricity (IV) comprising trivalent chromium, a (iv) salt thereof, and At least one source of divalent sulfur and substantially free of hexavalent chromium; 119773.doc -16 - 200806816 immersing a substrate in the electroplating bath; and applying chromium to the chromium to deposit crystalline chromium deposits on the substrate Sedimentary sedimentary crystals. The crystalline deposit in one embodiment has a lattice parameter of 2.8895 +/- 0_0025 angstroms obtained according to this method. * ^ In one embodiment, the crystalline chromium deposit obtained according to this method has a preferred orientation ("p〇,"). In another embodiment, the present invention provides a ^.u ^ ^ 禋 on a substrate Power-on deposition

A method of crystalline chromium deposits comprising the steps of: formic acid and substantially free of hexavalent to provide an electroplating bath comprising trivalent chromium chromium; immersing a substrate in the electroplating bath; and applying an electric current to deposit crystalline chromium Depositing on the substrate, wherein the chromium deposit is a crystalline state of deposition and the crystalline chromium deposit has a lattice parameter of 2 8895 + / 0.0025 angstroms. In the embodiment, the crystalline chromium deposit obtained according to the method has {111} preferred orientation. The methods of the present invention can be practiced under the conditions described herein and in accordance with standard test procedures for electroplating chromium. As described above, the source of divalent sulfur is preferably provided in the trivalent chromium plating bath. Various divalent sulfur-containing compounds can be used in accordance with the present invention. In one embodiment, the source of divalent sulfur may comprise one or a mixture of two or more of the following formula (I): wherein in (1), X1 and X2 may be the same or different and X1 and X2 are each Independently includes hydrogen, argin, amine, cyano, nitro, nitroso, azo, alkane 119773.doc -17- 200806816 carbonyl, methionyl, alkoxycarbonyl, aminocarbonyl, alkylamino Carbonyl, dialkylaminocarbonyl, carboxyl (as used herein, "carboxy" includes all forms of carboxyl groups, for example, carboxylic acids, alkyl carboxylates and carboxylates), carboxylates, sulfonates, Sulfite, phosphonate, phosphinate, sulfoxide, urethane, polyethoxylated alkyl, polypropoxylated alkyl, hydroxy, halogen-substituted alkyl, alkoxy, sulfuric acid a thiol group, a thiol group, a sulfinyl group, an alkyl sulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group are Ci-C ^, or X1 and X2 may form a bond from R1 to R2, thus forming a ring comprising R1 and R2 groups, wherein R1 and R2 may be the same or Different and R1 and R2 each independently include a single bond, an alkyl group, an allyl group, an alkenyl group, an alkynyl group, a cyclohexyl group, an aromatic and heteroaromatic ring, an alkoxycarbonyl group, an aminocarbonyl group, an alkylaminocarbonyl group, and two Alkylaminocarbonyl, polyethoxylated, and polypropoxylated alkyl, wherein the alkyl groups are Ci, C6, and wherein η has an average value between 1 and about 5. In the example, the divalent sulfur source may include one or a mixture of two or more of the following compounds of the formula (IIa) and/or (lib).

Wherein (IIa) and (lib), I, I, Han 5 and heart may be the same or different and independently include hydrogen, halogen, amine, cyano, nitro, nitroso, azo 117773.doc • 18· 200806816 base, calcined carbonyl, formyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, monoalkylamino, sulfhydryl, sulphate, yoghurt, phosphonate, phosphinate , sulfoxide, urethane group, polyethoxylated alkyl group, polypropoxylated alkyl group, hydroxyl group, dentate substituted alkyl group, alkoxy group, alkyl sulfate group, alkylthio group, alkane a sulfinyl group, an alkyl sulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group are Ci-C6 5 wherein X represents carbon, nitrogen, oxygen, Sulfur, selenium or tellurium and wherein m is between 0 and about 3, wherein η has an average value between 1 and about 5, and wherein (Ila) or (lib) each comprise at least one divalent sulfur atom. In one embodiment, the source of divalent sulfur may comprise one or a mixture of two or more of the following compounds of the formula (Ilia) and/or (Illb):

Wherein, in (Ilia) and (Illb), R3, R4, 115 and r6 may be the same or different and independently include hydrogen, halogen, amine, cyano, nitro, nitroso, azo, alkylcarbonyl, Mercapto, alkoxycarbonyl, aminocarbonyl, alkylamino, dialkylaminowei, sulfhydryl, sulphate, sulphate, sulphate, phosphinate, hydrazine, amine Acid ester group, polyethoxylated alkyl group, 119773.doc -19- 200806816 polypropoxylated alkyl group, hydroxyl group, alkyl group substituted by alkene, alkoxy group, thioxanthyl ester, alkylthio group Or alkylsulfinyl, alkylsulfonyl, phosphonic acid alkyl or phosphinate alkyl acrylate, wherein the alkyl and alkoxy are Ci-C6 ^ wherein X represents carbon, nitrogen, Sulfur, selenium or tellurium and wherein m is between 0 and about 3, wherein η has an average value between 1 and about 5, and wherein (Ilia) or (Illb) each comprise at least one divalent sulfur atom. In one embodiment, in any of the above sulfur-containing compounds, the sulfur may be replaced by selenium or tellurium. Exemplary selenium compounds include selenium-DL-methionine, selenocetine, other selenides (ie, R-Se_R,), diselectide (ie, R_Se-Se-R/), and sterol (ie, R-Se-H), wherein flanking, can independently be an alkyl or aryl group having up to about 20 carbon atoms, which can be similar to those described above with respect to sulfur, including other heteroatoms (eg, oxygen) Or nitrogen). Exemplary monumental compounds include ethoxy and methoxy-hoofed compounds, namely Te(〇C2H5)4 and Te(〇CH3)4. It should be understood that the substituents used are preferably selected so that the compound thus obtained remains soluble in the present invention. Invented in the electroplating bath. Comparative Example: Hexavalent Chromium A comparative example of various aqueous hexavalent chromic acid-containing electrolytes for the production of functional chromium deposits is set forth in Table 1 below, and the crystalline properties of the deposits are listed in the table and based on c, 〇, H, N and S analysis report element composition. H9773.doc -20- 200806816

Table 1 is used for electrolytes with functional chromium as hexavalent chromium

Lattice grain preferred orientation BCC random BCC (222) PO BCC BCC-SC BCC Lattice parameter volume of deposited state [〇] Atomic % Volume [H] Atomic volume [〇2] Atomic i Volume [s] Atomic % 2.883 2.882 BCC (222) (211) PO 2.883 0.055 0.078 0.36 0.62 (222) PO (110) P〇 random 2.881 0.04 0.076 0.84 0.04 2.882 0.06 0.068 0.98 0.12 2.886 The following table 2 lists the Ecochrome project as the most effective technology. A comparative example of a trivalent chromium process solution. The Ecochrome project is a European Union sponsored program (GlRD CT-2002-0071 8) to find an effective and high performance hard chrome alternative based on trivalent chromium (see Hard Chromium Alternatives Team (HCAT)). 119773.doc -21- 200806816

Meeting, San Diego, CA, Jan. 24-26, 2006). The three process solutions are from Cidetec, which is a Spanish consortium; ENSME, which is a French consortium; and Musashi, which is a Japanese consortium. In this table, if a chemical formula is not specifically listed, the material is considered to be the patented material for obtaining such data, and is not commercially available. Table 2 is based on the most effective conventional techniques of the functional trivalent chromium method of the Ecochrome project. EC1 (Cidetec) EC2 (ENSME) EC3 (Musashi) Cr(III) (Μ) 0.40 1.19 CrCl3.6H20 from Cr(OH)3+3HCl (Μ) 1.13 H2NCH2C02H (Μ) 0.67 Ligand 1 (Μ) 0.60 Body 2 (Μ) 0.30 Ligand 3 (Μ) 0.75 Η3Β〇3 (Μ) 0.75 Conductive salt (Μ) 2.25 HC02H (Μ) 0.19 NH4C1 (Μ) 0.19 2.43 Η3Β〇3 (Μ) 0.08 0.42 Α1〇3·6Η20 (Μ) 0.27 Surfactant cc / liter 0.225 0.2 pH 2-2.3 ~0·1 ~0·3 Temperature (°C) 45-50 50 50 Current Density A/dm2 20.00 •70.00 40.00 Cathode efficiency 10% ～27% 13% plated structure amorphous amorphous amorphous orientation NA ΝΑ 119 119773.doc -22 - 200806816 In the comparative example of Table 2, the EC3 example contains aluminum chloride. Other trivalent chromium solutions containing chlorinated compounds have been described. Suvegh et al. (Journal of Electroanalytical Chemistry 455 (1998) 69-73) uses 0·8 M [Cr(H20)4Cl2]C1.2H20, 0.5 Μ ΝΗ4α, 0·5 M Naa, 0.15 Μ Η3Β〇3,1 The pH of lysine and 0.45 Μ A1C13 electrolyte is not illustrated. Hong et al. (Plating and Surface Finishing, March 2001) describe an electrolyte having a pH of 1-3 comprising a mixture of formic acid, complex salt, boric acid, chlorinated clock and salt. Ishida et al. (Journal of the Hard Chromium Platers Association of Japan 17, No. 2, October 31, 2002) states that 1.126 Μ [(: γ(Η2Ο)4(:12](:1·2Η2Ο, 0·) A solution of 67 M glycine, 2.43 M NH4C1 and 0.48 M H3B 〇3, to which is added A1C13_6H20 in a quantity varying from 〇11-〇·41 ;; pH is not illustrated. In the four disclosed trivalent chromium baths In the reference for aluminum chloride, only Ishida et al. claimed that the chromium deposit was crystalline, which states that the crystalline deposit system is produced with an increase in the concentration of A1C13. However, the inventors replicated the test and produced a repeat of the crystalline deposit. The attempt failed. It is believed that an important test variable, Ishida et al., did not elaborate. Therefore, Ishida et al. were not able to teach how to produce reliable and consistent crystalline chromium deposits. Table 3 lists various water-based ("T" An electrolyte containing trivalent chromium and an ionic liquid ("IL") an electrolyte containing trivalent chromium, all of which can produce chromium deposits having a thickness of more than 1 micrometer and list the crystalline properties of the deposit In the table. 119773.doc -23- 200806816 Table 3 for functional chromium with trivalent chromium-based electrolyte T1 T2 Τ3 Τ4 Τ5 Τ6 Τ7 IL1 MW Cr(0H)S04. Na2S040 (Μ) 0.39 0.39 0.39 0.55 0.39 307 KC1 (Μ) 3.35 74.55 h3bo3(m ) 1.05 61.84 HC02'K+(M) 0.62 84.1 CrCl36H20 1.13 2.26 266.4 (M) Cr(HC02)3 0.38 187 (M) CH2OHCH2 2.13 139.5 (M) NH4CH02(M) 3.72 5.55 63.1 LiCl (M) 2.36 42.4 HC02H (M 3.52 3.03 3.52 0.82 4.89 46.02 NH4OH (M) 5.53 4.19 5.53 35 (nh4)2so4 0.61 0.61 1.18 132.1 (M) NH4CI (M) 0.56 0.56 1.87 0.56 0.56 53.5 NH4Br (M) 0.10 0.10 0.51 0.10 0.10 0.10 97.96 Ν^4Ρ2 〇7" 10 0.034 0.034 0.034 446 H20 (M) KBr (M) 0.042 119 h2o Make up to make up the foot to make up the foot to make up the full without 18 to 1 to 1 to 1 to 1 to 1 to 1 to 1 to 1 liter Lit up and rise 119773.doc •24- 200806816 pH 0.1-3 0.1-3 0.1-3 0.1-3 0.1-3 0.1-3 0.1-3 NA Current density (A/dm2) 12. 4 20 20 20 20 50 80 Temperature, °c 45 45 45 45 45 45 45 80 Cathode efficiency 25% 15% 15% 15% 15% 30% About 10% Lattice Amor. Amor. Amor. Amor. Amor. NA sc grain preferred orientation ΝΑ NA NA NA NA Pwdr Pwdr Rndm 4 hours / 19l °c Annealed lattice parameter 2.882 2.884 2.882 2.886 2.883 NA NA - organically added J pH>4 Amor. xtal. xtal· xtal. Xtal. xtal. xtal. Grain orientation (111), Rndm (111), Rndm (111), Rndm (111), Rndm (111), Rndm (111), Rndm electrolyte + A1C13*6H20 0.62 Μ, ρΗ<3 Xtal. xtal. xtal. xtal. xtal. xtal. (In Table 3: pwdr = powder; Amor. = amorphous open; rndm = random; NA = not applicable; SC = simple cubic; xtal. = Crystallization) In Table 4, the sediments from Tables 1, 2, and 3 were compared using standard test methods commonly used to evaluate deposited functional chromium electrodeposits. It can be observed from this table that amorphous deposits, and deposits that are not BCC (body-centered cubic) cannot pass all necessary initial tests. 119773.doc -25- 200806816 Table 4 Comparison of Test Results of Deposited Functional Chromium from Electrolytes in Table 1-3 Electrolyte Structure Directional Appearance Grinding Test Large Crack Hardness after Heating Vickers (100 g) Cracks Caused by Depression H1 BCC Random powder failure - H2 BCC (222) Glossy qualified No 900 No H3 BCC (222) (211) Glossy qualified No 950 No H4 BCC (222) Glossy qualified No 950 No H5 BCC+ SC (222) (110) Gloss failure No 900 No H6 BCC Random Gloss Failure No 960 EC1 amor. ΝΑ Glossy failure has 845-1000 with EC2 amor. ΝΑ Glossy failure has 1000 EC3 amor. ΝΑ Glossy failure has - There is T1 amor. ΝΑ Glossy failure has 1000 T2 amor. ΝΑ Glossy failure has 950 T3 amor. ΝΑ Glossy failure has 950 T4 amor. ΝΑ Glossy failure has 900 T5 amor. ΝΑ Glossy failure has 1050益T6 amor. ΝΑ Glossy failure has 950 T7 powdery — — — — IL1 SC random black particle failure has — based on substitution Industry needs chromium electrodeposition bath, the deposit of the product from a trivalent chromium bath electrodeposition 119773.doc -26- 200806816 valid and must be based crystals as a functional chromium deposit. It has been discovered that certain additives can be used in conjunction with the adjustment of the process variables of the electrodeposition process to obtain a desired crystalline chromium deposit from a trivalent complex bath substantially free of hexavalent chromium. Typical process variables include current density, solution temperature, solution agitation, additive concentration, control of the applied current waveform, and solution pH. Each additive test can be used to correctly estimate the specific additive efficiency, including, for example, x-ray diffraction (XRD) (to study the structure of the chromium deposit, X-ray photoelectron spectroscopy (XPS) (for The composition of the chromium deposit is determined to be greater than about 0.2-0.5% by weight, elastic rebound determination (ERD) (for determining gas content), and electron microscopy (for determining physical or morphological characteristics, such as cracks). Technical towels, usually and widely derived from the chrome deposit of the San Mi bath must be implemented at a pH of less than about 2.5, however, the system isolating the three-valent road money processing process, which includes a brush plating process, in which a higher yang is used, but The higher cation used in the brush plating scheme cannot obtain crystalline chromium deposits. Therefore, in order to evaluate the efficiency and stability of various additives, high-electrolytes and generally recognized low-pH electrolytes were tested. 119773.doc 27- 200806816 5: Additive concentration range of additive additive induced from T2 crystallization from trivalent chromium bath Τ2 pH 2.5: Is it crystallized? T2 pH 4.2: Is it crystallized? Methionine 0.1, 0.5, 1.0, 1.5 g/liter No Yes, yes, na cystine 0.1, 0.5, 1.0, 1.5 g / liter No, yes, yes, is thiophene 0.1, 0.5, 1, 1.5, 2, 3 ml / liter No No, no, yes Yes, yes, is thiodipropionic acid 0.1, 0.5, 1.0, 1.5 gram / liter No No, yes, yes, thiodiethanol 0.1,0·5, 1-0, 1.5 g / liter No No, yes, yes, is cysteine 0.1,1,2.0, 3.0 g / liter No, yes, yes, is fine propyl sulfide 0.5, 1.0, 1.5 ml / liter No No, yes, yes, na sulfur Sub-salicylic acid 0.5, 13 1.5 No, yes, is 3J-dithiodipropionic acid 1,2, 5, 10 g / liter No, yes, yes, is tetrahydrothiophene 0.5, 1.0, 1.5 ml / Whether the liter is negative or not, according to the data shown in Table 5, it is apparent that when the chromium is electrodeposited from the trivalent chromium solution at about the above concentration and when the pH of the bath is greater than about 4, there are two in its structure. The sulphur-containing compound induces crystallization, wherein the chromium crystal according to the invention has a lattice parameter of 2.8895 +/- 0.0025 angstroms. In one embodiment, other divalent sulphur compounds may be used in the baths described herein for electrodeposition. Crystalline chromium of the lattice parameters of the present invention. In one embodiment, chromium crystals are also induced when a compound having sulfur, selenium or tellurium is used as described herein. In one embodiment, the selenium and tellurium compounds correspond to the above The identified sulfur compounds, and like 119773.doc -28 - 200806816, as with the sulfur compounds, resulted in the electrodeposition of crystalline chromium having a lattice parameter of 2.8895 +/- 0.0025 angstroms. To further illustrate the induction of such crystallization, electrolyte D3 was used at pH 5.5 and at a temperature of 5 Torr. A study using a brass substrate for the crystallization-inducing additive using the same cathode current density of 40 A/dm2 and a plating time of 3 minutes was reported in Table 6 below. After the plating is completed, X-ray diffraction, radiation-induced X-ray fluorescence is used to measure the thickness, and electron-induced ray-ray fluorescence is combined with an energy discrete spectrophotometer to measure the sulfur content to test the sample. Table 6 summarizes these data. This data indicates that not only is there a divalent sulfur compound present in the solution at a concentration exceeding the critical concentration for inducing crystallization but also sulfur is present in the deposit. Table 6: Induction of sulfur from various divalent sulfur additives and effect on Cr-plated crystallization and plating rate of Cr+3 solution

H9773.doc -29- 200806816 1.5 ml is 2.68 6.7 2 ml is 4.56 7.8 3 ml is 6.35 7.1 thiodipropionate · 1 g no 6.73 1 0.5 g is 4.83 3.5 1.0 g is 8.11 1.8 1.5 g is 8.2 3.1 sulfur Substituted diethanol 0. 1 ml No 4.88 0.8 0.5 ml is 5.35 4 1.0 ml is 6.39 4 1.5 ml is 3.86 4.9 Cysteine 0.1 g is 2.08 5.1 1.0 g is 1.3 7.5 2.0 g is 0.35 8.3 3.0 g is 0.92 9.7 晞Propyl sulphate 0.1 ml No 6.39 1.3 (Oil) 0.5 ml is 4.06 3.4 1.0 ml is 1.33 4.9 1.5 ml (insoluble) 5.03 2.6 thiosalicylic acid 0.5 g is 2.09 5.8 1_ gram is 0.52 5.5 1_5 gram is 0.33 7.2 1.5 g is 0.33 7.2 3, 3'-thiodipropionic acid 1 g is 7.5 5.9 2 g is 6 6.1 5 g is 4 6 10 g is 1 6.2 (S content is determined by EDS) 119773.doc • 30- 200806816 (" (insoluble) means that the additive is saturated at a given concentration.) Table 7 provides additional data regarding the trivalent chromium plating bath according to the present invention. Table 7 is used to prepare deposited crystalline Cr from a Cr+3 solution. Representative formulation. Electrolyte additive pH-0C· A/dm2 Cathodic efficiency better orientation Hv [C] [S] [Ν] P1 T2 4 ml / liter thiophene 5.5-50-40 5-10% (222) 900- 980 3.3 1.57 0.6 P2 T2 3 ml / liter thiodiethanol 5.5-50-40 10% random and (222) - 3.0 1.4 0.6 P3 T2 1 g / liter 1-cysteine 5.5-50-40 5% random and (222) - P4 T5 4 ml / liter thiophene 5.5-50-40 5-10% (222) 900- 980 P5 T5 3 ml / liter thiodiethanol 5.5-50-40 10% random and (222 ) - P6 T5 1 g / liter 1-cysteine 5.5-50-40 5% random and (222) - P7 T5 4 ml / liter thiophene 5.5-50-40 15% (222) 900- 980 P8 T5 3 ml / liter sparse diethanol 5.5-50-40 10-12% random and (222) - P9 T5 1 g / liter 1-cysteine 5.5-50-40 7-9% random and (222) P10 T5 2 g / liter thiosalicylic acid 5.5-50-40 10-12% (222) 940- 975 5.5 1.8 1.3 P11 T5 2 g / liter 3,3 '- two stone waste dipropionic acid 5.5-50-40 12-15% (222) 930- 980 4.9 2.1 1.1 119773.doc -31 - 200806816 The above examples all use DC without using complex cathode waveforms (eg pulsation or cycle) Counter-pulsation plating) was prepared, but those changes are applied within the scope of the invention (iv). All of the examples in Table 7 are negative two, , and σ. The example deposition states have a lattice constant of 2.8895 + Λ 0.0025 angstrom. In the other real money of the present invention, the pulse (4) (4) enables (4) a single pulsation waveform to be implemented with or without sulphur, which is equipped with a power enhancement interface and a Kepc 〇 bipolar +/_ι〇Α Power is produced by the Princeton Applied Researeh 273Α potentiostat. The pulsating waveform is a rectangular wave with a 5 〇 % duty cycle and a sufficient current to produce a total current density of 4 〇 A/dm 2 . The frequency used is 〇·5 Hz, 5 Ηζ, 5〇 Ηζ^5〇〇

Hz. At all frequencies, the deposit is amorphous in the absence of thiomorpholine according to the method ρι, and according to the method 在 in the case of thiomorpholine, the deposit is crystalline. In other examples of the use of the invention, the pulsation deposition is performed using a simple pulsation waveform using method P1 with or without thiophene, which utilizes a power enhancement interface and a KepC0 bipolar +/- 10A power supply. Produced by the Princeton Applied Research Model 273A potentiostat. The pulsating waveform is a rectangular wave with a 50% duty cycle and sufficient current to produce a total current density of 4 〇 A/dm2. The frequencies used are 〇 5 Hz, 5 Hz, 50 Hz and 500 Hz. At all frequencies, according to method P1, in the absence of thiomorpho, the deposits are amorphous, according to the method? 1 In the presence of thiomorpholine, the deposits are in the as-deposited state and have a lattice constant of 2.8895 +/- 0.0025 angstroms. Similarly, electrolyte T5 was tested at various concentrations of 2 119773.doc • 32 - 200806816 g/L with or without thiosalicylic acid using a variety of pulsating waveforms of 66-109 A/dm2. The current range, wherein the pulsation duration is from 0.4 to 200 milliseconds and the rest time is 0.1 to 1 millisecond, including a periodic inverse waveform having a counter current of 38-55 A/dm2 and a duration of 0.1-2 milliseconds. In all cases, in the absence of thiosalicylic acid, the deposit is amorphous 'the crystallization is in the case of thiosalicylic acid' and has a lattice of 2.8895 +/- 0.0025 angstroms Constants In one embodiment, 'these crystalline deposits are homogeneous' have no intentionally entrapped particles and have a lattice constant of 2.8895 + Λ 0.0025 angstroms. By way of example, particles of alumina, Teflon, tantalum carbide, tungsten carbide, titanium nitride, and the like can be used with the present invention to form crystalline chromium deposits comprising such particles in the deposit. The particle systems used with the present invention are substantially carried out in the same manner as known from prior art methods. The above examples use a platinum titanium anode. However, the invention is in no way limited to the use of such anodes. In one embodiment, a graphite anode can be used as the insoluble anode. In another embodiment, a soluble chromium or chrome-iron anode can be used. In an embodiment, the anodes can be isolated from the bath. In one embodiment, the anodes can be isolated by using a fabric that can be tightly knitted or loosely woven. Suitable fabrics include those of ordinary skill in the art for use in this application, including, for example, cotton and polypropylene, the latter being available from Chautauqua Metal Finishing Supply, Ashville, NY. In another embodiment, the anode can be isolated by using an anionic or cationic membrane, such as a perfluorosulfonic acid membrane sold under the tradenames NAFION® (DuPont), AC1PLEX® (Asahi Kasei), FLEMION® (Asahi Glass) or Others are supplied by Dow 119773.doc -33- 200806816 or by Membranes International Glen R〇ck (NJ). In one embodiment, the anode can be placed in a compartment wherein the compartment is filled with an acid exchange device (eg, a cationic or anionic membrane or a salt bridge) that is acidic, neutral, or Alkaline electrolyte. Figure 1 includes three X-ray diffraction patterns (Cu k α) of crystalline chromium deposited according to an embodiment of the invention and using hexavalent chromium of the prior art. The 1 ray diffraction pattern is at the bottom and The middle consists of 2 g/liter (bottom) and 10 g/liter (intermediate) 3,3,_dithiodipropene (DTDp) acid deposited in a trivalent chromium bath from a 2 4 chrome electrolyte T5. Chromium. Each of these samples is deposited using the same deposition time and current density. In contrast, the top sample is from a conventional chromium deposit of the eight-electrolyte electrolyte H4 (described above), as shown by the top and bottom scans, for In both cases of hexavalent chromium and 2 g/LDT DTDp, no brass substrate peaks (marked with (*) for intermediate scanning; see also Figure 9 and the original text) indicate thick deposits greater than about 2 〇micron (Cu匕 penetrates through the chrome In contrast, the presence of a brass peak at 1 gram per liter of DTDp indicates that excess DTDP can reduce cathode efficiency. However, in both DTDP cases, strong and broad (222) reflections indicate strong presence. {111} is preferably oriented and the continuous diffraction domain of chromium (generally considered to be related to particle size) is extremely small and similar to chromium from the hexavalent process H4. Figure 2 is typical of amorphous chromium from prior art trivalent chromium baths.乂 _ ray diffraction pattern (Cu k α). As shown in Figure 2, there is no peak corresponding to the regular occurrence of atoms in the structure, if the chromium deposit is crystalline, a spike should be observed. ~ Figure 3 A series of typical X-ray diffraction patterns (Cu k α) showing the progressive effect of annealing of amorphous chromium deposits from the prior art trivalent chromium bath (without sulfur) from 119773.doc -34-200806816. A series of x-ray diffraction scans are shown in Figure 3, and in Figure 3, the upward graph refers to the case where the chromium deposits are subjected to longer and longer annealing times. The initial 5 Hai amorphous road deposits are obtained as shown in the scheme. Similar to the X-ray diffraction pattern of Figure 2, but with continued retreat The chromium deposit gradually crystallizes, which results in a pattern corresponding to the peak of the regularly occurring atom in the ordered crystal structure. The lattice parameter of the annealed chromium deposit is in the range of 2.882 to 2 885, although the quality of the series is not good. Sufficient to make the measurement accurate. One = 4 series - series electron microscopy μ, which shows the large crack effect of annealing an initial amorphous chromium deposit from a prior art trivalent chromium bath. In the photomicrograph of the crystalline chromium, the chrome layer is deposited on a light-colored layer on the mottled-substrate substrate. In the photomicrograph labeled "at 250" hour, at 250. (: under annealing 丨 hours Thereafter, a large crack is formed while the chromium deposit crystallizes, and the large cracks extend through the thickness of the chromium deposit up to the substrate. In this and subsequent photomicrographs, the interface between the chromium deposit and the substrate is substantially perpendicular to the blurring boundary of the propagation of the large cracks, and is identified by a small black square with "P1". In the photomicrograph of π at 350 ° C for 1 hour, after annealing for 1 hour at 35 °t:, a larger and more determined large crack is formed (compared with " in hours, compared to the sample), The chromium deposits crystallize and the large cracks extend through the thickness of the chromium deposit up to the substrate. In the photomicrograph labeled "i hours" at 45 〇t, annealed at 45 (TC) After an hour, the large cracks are formed and the sample is larger at a lower temperature, while the chromium deposit crystallizes, the large cracks extending through the thickness of the chromium deposit up to the substrate. At the mark, at 55〇<;t H9773.doc -35- 200806816 In the photo of the next hour ", after annealing at 550 ° C for 1 hour, these large cracks are formed and it seems that the temperature sample must be lower, and Crystallization of chromium deposits through which the large cracks extend Thickness up to the substrate. Figure 5 shows a typical χ-ray diffraction pattern (Cu k α) of a deposited crystalline chromium deposit according to the present invention. As shown in Figure 5, the ray diffraction peaks are sharp and clearly defined This indicates that the chromium deposit crystallizes according to the invention.

Figure 6 shows a typical χ-ray diffraction pattern (Cu k α) of a crystalline chromium deposit according to the present invention. The middle two χ·ray diffraction patterns shown in Figure 6 show a strong (222) peak, which indicates that the {111} preferred orientation (ρ〇) is similar to that observed with crystalline chromium deposited from a hexavalent chromium bath. of. The top and bottom X-ray diffraction patterns shown in Figure 6 include (2 〇〇) peaks indicating the preferred orientation observed for other crystalline chromium deposits. Figure 7 is a graph showing the relationship between the sulfur concentration and the crystallinity of chromium deposits in the chromium deposit-embodiment. In the graph shown in Fig. 7, the crystallinity axis is designated as a value if the deposit is a crystal, and the crystallinity axis is designated as a value 若 if the deposit is amorphous. Therefore, in the embodiment shown in FIG. 7, when the sulfur content of the chromium deposit is from about 17% by weight to about 4% by weight, the deposit is crystallized, and outside the core, (4) (four) is amorphous ^ ' In other words, the amount of sulfur present in a given crystalline chromium deposit can vary. In other words, in the case of the bismuth yoke, a crystalline chromium deposit may be coated (for example, "the weight of the sulphur is deflated, and in other embodiments (4), the deposit having the sulphur content may be amorphous. (As shown in FIG. 7 , in his embodiment, for example, H9773.doc -36-200806816 can be found in the crystallization complex as a rain, up to about 1% by weight of the higher sulfur content, and In other embodiments, if the sulfur content is greater than 4% by weight, the deposit may be amorphous. Therefore, the sulfur content is extremely important, but is not a variable that controls and affects the crystallinity of the trivalent-derived chromium deposit. A graph comparing the crystal enthalpy parameters (expressed in angstroms), which will be carried out according to the crystalline chromium deposit of the present invention and the crystalline chromium deposits from the hexavalent chromium bath and the annealed as-form amorphous chromium deposits. Comparing. As shown in Fig. 8, the present invention has a lattice of aa chrome; the lattice parameter of the cherries is significantly larger than that of the chromium obtained by pyrometallurgy ("PyroCr"), and is substantially different from The lattice parameters of all hexavalent chromium deposits are large and Significantly different, and significantly more lattice parameters than the annealed deposited amorphous chromium deposits ("T1 (350 ° C)", "T1 (450 ° C), 'and " T1 (550 ° C),) Large and distinctly different. The difference between the lattice parameters of the trivalent crystalline chromium deposit of the present invention and the crystal parameters of other chromium deposits (such as those depicted in Figure 8) is valid, according to the standard. Study "t, test at least 95% confidence level. Figure 9 is a typical χ-ray diffraction pattern (Cu k α) showing the progressive effect of an increase in the amount of thio-salicylic acid, which is shown in accordance with an embodiment of the present invention. Reliable consistent (222) reflection of the crystalline chromium deposits of the trivalent chromium bath, (η) preferred orientation. In Figure 9, the crystalline chromium system utilizes a nominal 2-6 g/L thiosalicylic acid (over 罝140 AH/L) electrolyzed from a trivalent chromium electrolyte T5 (as described above) at 1 ampere/liter (A/L) onto a brass substrate (from the peak of brass (*)) This demonstrates reliable (222) reflection, {111} preferred directional deposits. These samples were obtained at approximately 14 。 intervals. H9773.doc -37- 200806816 In one embodiment, the cathode efficiency is between about 5% and about 8%, and in one embodiment the 'cathode efficiency is between about 1% and about 4,000%, and in another In one embodiment, the cathode efficiency is between about 1% and about 30%. In another embodiment, the crystalline chromium electrodeposit (wherein the chromium has a crystal constant of 2.8895 +/- 0.0025 angstroms) Additional alloying can be carried out using ferrous sulfate and sodium hypochlorite as sources of iron and phosphorus with or without an additional 2 g/L of thiosalicylic acid. 〇·1 g/L to 2 g/L Ferrous ions are added to the electrolyte T7 to obtain an alloy containing 2-20% of iron. These alloys are amorphous in the presence of thiosalicylic acid. An alloy containing 2-12% of phosphorus in the deposit was obtained by adding 1-2 g/L of sodium hypophosphite. These alloys are amorphous unless thiosalicylic acid is added. In another embodiment, the crystalline chromium/integral having a lattice constant of 2.8895 +/- 〇·0 〇 25 Å is derived from an electrolyte having 2 g/liter of thiosalicylic acid Τ7 using ultrasonic energy. Frequency agitation at 25 kHz and 0.5 MHz is obtained. The resulting deposits had a lattice constant of 2·8895+/·〇·〇〇25 Å, and the deposition rate did not change significantly regardless of the frequency used. It should be understood that throughout the specification and claims, the numerical limits of the disclosed ranges and ratios can be combined and are considered to include all intermediate values. Therefore, for example, when the specific disclosure range ^(8) and 1〇_5〇, the range 110 I*"50, 10-100, and 5〇-100 are considered to be within the same range as the intermediate integer value. Inside. Moreover, it is believed that all values are preceded by a modification, whether or not the term is a particular statement. Moreover, when the chromium deposit is electrodeposited from a trivalent chromium bath as disclosed herein, and thus formed When the sediment system is crystallized as described herein, the lattice constant is considered to be 119773.doc -38 - 200806816 2.8895 +/- 0.0025 angstroms, regardless of whether the lattice constant is specifically stated. Finally, the disclosed elements and components are considered All possible combinations are within the scope of the disclosure, whether or not specifically recited. Although the principles of the present invention have been explained for some specific embodiments and are provided for the purpose of the present disclosure, it should be understood that after reading this specification It will be apparent to those skilled in the art that the present invention is to be construed as being limited to the scope of the claims. The scope of the present invention is limited only by the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 includes two χ-ray diffraction patterns (Cu) of crystalline chromium deposited by hexavalent chromium according to an embodiment of the present invention. k α) Figure 2 is a typical χ•ray diffraction pattern (Cu k (X) from amorphous chromium of the prior art trivalent chromium bath. Figure 3 is a typical X-ray diffraction pattern (Cu ka), which shows Asymptotic effect of annealing of amorphous chromium deposits from prior art divalent chromium baths. Figure 4 is a series of electron micrographs showing large cracks that anneal an initial amorphous chromium deposit from a prior art trivalent complex bath. Figure 5 is a typical X-ray diffraction pattern (CU ka) of a deposited crystalline chromium deposit according to an embodiment of the invention. Figure 6 is a series of typical X-rays of crystalline chromium deposits in accordance with one embodiment of the present invention. Diffraction pattern (Cllka). Figure 7 is a graph showing the relationship between sulfur concentration and crystallinity of chromium deposits in one embodiment of chromium deposits. Figure 8 is a comparison of lattice parameters (expressed by angstrom (A) a graph of 119773.doc -39 - 200806816 according to an embodiment of the invention, a crystalline chromium deposit and (2) a crystalline chromium deposit from a hexavalent chromium bath and (3) an annealed as-form amorphous chromium The sediments were compared. Figure 9 shows an increase in the amount of non-thiosalicylic acid. A typical 乂-ray % shot pattern (Cu k α) of the progressive effect, which exhibits a reliable consistent (222) reflection, (111) preferred orientation from a three-spoke chromium cold crystalline chromium deposit in accordance with an embodiment of the present invention. It should be understood that the process (four) and structure disclosed in the following paragraphs do not constitute a complete process flow for manufacturing a component comprising the functional crystalline chromium deposit of the present invention. The present invention can be implemented in conjunction with the manufacturing techniques currently used in the art, and they are commonly used. The process steps are hereby incorporated by reference to the needs of the present invention.

119773.doc 40·

Claims (1)

200806816 X. Patent application scope: A crystalline chromium deposit having a lattice parameter of 2.8895 +/- 0.0025 angstroms. . 2. The crystalline chromium deposit of claim 1, wherein the chromium deposit is electrodeposited from a trivalent chromium bath. The crystalline chromium deposit of claim 1 further comprising carbon, nitrogen and sulfur in the chromium deposit. 4. A crystalline chromium deposit as claimed in claim 3, wherein the chromium deposit comprises from about 1% by weight to about 1% by weight of sulfur. The crystalline chromium of item 3, wherein the chromium deposit comprises from about 1 to about $% by weight of nitrogen. 6. The crystalline chromium of claim 3, wherein the chromium deposit comprises carbon in an amount less than the amount that causes the chromium deposit to become amorphous. 7. The crystalline chromium deposit of claim 3, wherein the deposit comprises from about 7% by weight to about 4% by weight sulfur, from about 1% by weight to about 3% by weight nitrogen and about 0.1 weight % to about 10 weights c/❶ of carbon. 8. The crystalline chromium deposit of claim 1, wherein the deposit is substantially free of large cracks. 9) The crystalline chromium deposit of claim 1, wherein the chromium has a {111} preferred orientation. The article comprises a crystalline chromium deposit, wherein the crystalline deposit has a crystal of 2.8895 +/- 0.0025 angstroms. Grid parameters. 11. The article of claim 10, wherein the chromium deposit has {(1)} preferred orientation 0 119773.doc 200806816 12. The article of claim 1 and sulfur. Wherein the chromium > redundancy further comprises carbon nitrogen 13. - a method of electrodepositing crystalline chromium deposits on a substrate, comprising: long: for a money bath, the table will be bivalent, 匕 3 - 1 shell An organic additive and at least one source of divalent sulfur, and substantially free of hexavalent chromium; immersing a substrate in the electric forging bath; and applying a motor to deposit a crystalline chromium deposit on the substrate, wherein the chromium Sediment systems are crystalline when deposited. 14. The method of claim 13, wherein the crystalline collateral deposit has a lattice parameter of 2 Jane + / 0 0 0 2 5 angstroms. The method of claim 13, wherein the crystalline chromium deposit has a preferred orientation of 丨111丨. The method of claim 13, wherein the chromium deposit further comprises carbon, nitrogen and sulfur in the chromium deposit. 17. The method of claim 16, wherein the chromium deposit comprises from about j% by weight to about 10% by weight sulfur. 18. The method of claim 16, wherein the chromium deposit comprises from about 1 to about 5 weight percent nitrogen. The method of claim 16, wherein the chromium deposit comprises a quantity of carbon that is less than an amount that causes the chromium deposit to become amorphous. 20. The method of claim 16, wherein the deposit comprises about io.7 by weight. /❶ to about 4% by weight of sulfur, about 5% by weight to about 3% by weight of nitrogen and from about 1% by weight to about 10% by weight of carbon. The method of claim 13, wherein the deposit is substantially free of large cracks. 119773.doc 200806816 22. The method of claim π, wherein the electroplating bath further comprises ammonium hydroxide or a salt or a primary, secondary or tertiary amine. The method of claim 13, wherein the electroplating bath has a pH of from 4 to about 6.5. 24. The method of claim 13, wherein the electroplating bath system is at about 35. 〇 to a temperature of about 95 ° C. 25. The method of claim 13, wherein the current is applied at a current density of at least about 1 ampere amperage per square meter (A/dm2). The method of claim 13, wherein the current is applied using any one of a direct current, a pulsating waveform, or a pulsating periodic inverse waveform, or a combination of two or more thereof. The method of claim 13, wherein the divalent sulfur source comprises one or a mixture of two or more of the following formula (Ϊ): XLRi-XSVR^X2 (I) wherein in (I) X1 and X2 may be the same or different and X1 and X2 each independently include hydrogen, _ s, amine, cyano, nitro, nitroso, azo, alkyl, fluorenyl, alkoxycarbonyl, amine Carbocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, carboxyl, sulfonate, sulfinate, phosphonate, phosphinate, sulfoxide, urethane, polyethoxylated alkyl, Polypropoxylated alkyl, perylene, halogen-substituted alkyl, alkoxy, alkyl sulfate, alkylthio, alkyl sulphate, alkylsulfonyl, phosphine An acid alkyl ester group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group, or X1 and X2 together form a bond from R1 to R2, 119773.doc 200806816 wherein R1 and R2 are Identical or different and Ri and R2 each independently include a single bond, an alkyl group, a dipropyl group, an alkenyl group, a fast group, a cyclohexyl group, an aromatic and heteroaromatic ring, a oxycarbonyl group, a carbonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group, a polyethoxylated group, and a polypropoxylated alkyl group, wherein the alkyl group is CKC6, and wherein η has an average of from 1 to about 5 value. 28. The method of claim 13, wherein the divalent sulfur source comprises one or a mixture of two or more of the compounds of the following formula (Ila) and/or (lib): R4v^Sk^R5 and / Or into Re (Ila) Wherein (Ila) and (lib), R3, R4, 115 and R6 may be the same or different and independently include hydrogen, a hydroxyl group, an amine group, a cyano group, a nitro group, a nitroso group, an azo group, an alkylcarbonyl group. , mercapto, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, buffer, sulphate, yoghurt, phosphonate, phosphinate, sulfoxide, urethane Ester group, polyethoxylated alkyl, polypropoxylated alkyl, perylene, calcinin-substituted alkyl, alkoxy, alkyl sulfate, alkylthio, alkylsulfinyl, alkane a sulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group, wherein X represents carbon, nitrogen, oxygen, sulfur, selenium or tellurium and wherein m is derived from 0 to 119773.doc 200806816 about 3, wherein η has an average value from 1 to about 5, and wherein (Ila) or (lib) each includes at least one divalent sulfur atom. 29. The method of claim 13 wherein the source of divalent sulfur comprises one or a mixture of two or more of the following compounds of the formula (Ilia) and/or (Illb): R4 twist line yR5 A丄Rs and 'or iIIIa> (Illb) wherein, in (Ilia) and (Illb), &, I, and oxime may be the same or different and independently include hydrogen, halogen, amine, cyano, nitro , nitroso, azo, alkylcarbonyl, decyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, carboxyl, sulfonate, sulfinate, phosphonate, sub Phosphonate, sulphur, urethane, polyethoxylated alkyl, polypropoxylated alkyl, thiol, alkoxy, alkyl sulfate, alkane a thio group, an alkylsulfinyl group, an alkylsulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group are CCK6, wherein X represents carbon, nitrogen, Sulfur, selenium or tellurium and wherein m is from about 3 to 3, wherein η has an average value from 1 to about 5, and wherein (Ilia) or (Illb) each comprise at least one divalent sulfur atom. 30. The method of claim 13 wherein no large cracks are formed when the crystalline chromium deposit is heated to a temperature of up to about 300 °C. 119773.doc 200806816 31. A method of electrodepositing a crystalline chromium deposit on a substrate to provide an electroplating bath comprising trivalent chromium and no hexavalent chromium thereon; the method comprising: an organic additive, and substantially immersing a substrate in In the electroplating bath; and applying an electric current to deposit a crystalline chromium deposit on the substrate. The chromium deposit is in a crystalline state when deposited and the crystalline chromium has a lattice parameter of 2.8895 + Λ 0.0025 angstrom. Where the sediment 32_ Method as requested in item 31. j ' wherein the crystalline chromium deposit has (i j j ) preferably 33. The method of claim 31, wherein the deposit in the chromium deposit further comprises carbon, nitrogen and sulfur. 34. The method of claim 33, wherein the chromium deposit comprises from about 1 weight ❶/❶ to about 10% by weight sulfur. The method of claim 3, wherein the chromium deposit comprises from about 1 to about $% by weight of nitrogen. 36. The method of claim 33, wherein the chromium deposit comprises a quantity of carbon that is less than an amount that causes the chromium deposit to become amorphous. The method of claim 33, wherein the deposit comprises from about 17% by weight to about 4% by weight ❶/α of sulfur, from about 重量% by weight to about 3% by weight of nitrogen, and from about 1% by weight to about 10% by weight. ❶ / Q carbon. 38. The method of claim 31, wherein the deposit is substantially free of large cracks. The method of claim 31, wherein the electroplating bath further comprises ammonium hydroxide or a salt, or a primary, secondary or tertiary amine. 40. The method of claim 31, wherein the electroplating bath has a pH of from 119773.doc 200806816 from 45 to about 6.5. 41. The method of claim 31, wherein the electroplating bath is in a self-contained. . To a temperature of about 95 ° C. 42. The method of claim 31, wherein the current is applied at a current density of at least about 1 ampere amperage per square meter (A/dm2). 43. The method of claim 31, wherein the current is applied using a direct current, a pulsating waveform, or a pulsating periodic inverse waveform. The method of claim 3, wherein the electroplating bath further comprises a divalent sulfur source comprising one or a mixture of two or more of the following compounds of the formula (I): X1-R1-(S) n-R2-X2 (I) wherein in (I), X1 and X2 may be the same or different and X1 and X2 each independently include hydrogen, halogen, amine, cyano, nitro, nitroso, azo, Alkylcarbonyl, methionyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, carboxyl, sulfonate, sulfinate, phosphonate, phosphinate, sulfoxide, amine Acid ester group, polyethoxylated alkyl group, polypropoxylated alkyl group, mercapto group, halogen-substituted alkyl group, alkoxy group, sulfuric acid alkyl ester, sulfur-burning group, alkyl group, sulphur group a thiol group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group (^-<:6, or X1 and X2 may form from R1 to R2 a linkage, wherein R1 and R2 may be the same or different and R1 and R2 each independently comprise a single bond, an alkyl group, an allyl group, an alkenyl group, an alkynyl group, a cyclohexyl group, an aromatic and heteroaromatic ring, a oxycarbonyl group, An aminocarbonyl group, an alkylamino group, a dialkylaminocarbonyl group, a polyethoxylated group, and a polypropoxylated alkyl group, wherein the alkyl group 119773.doc 200806816 is a Ci-C6 group, and wherein The method of claim 31, wherein the electroplating bath further comprises one or both of the compounds having the following formula (Ila) and/or (IIb) or Source of divalent sulfur of the above mixture: Wherein (Ila) and (lib), Rule 3, Disgust 4, 1^5 and 6 may be the same or different and independently include hydrogen, halogen, amine, cyano, nitro, nitroso, azo Base, alkylcarbonyl, decyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, carboxyl, sulfonate, sulfinate, phosphonate, phosphinate, sulfoxide, amine Carbamate-based, polyethoxylated alkyl, polypropoxylated alkyl, hydroxyl, dentate-substituted alkane, alkoxy, alkyl sulfate, alkylthio, alkylsulfin Alkyl, alkylsulfonyl, alkyl phosphonate or alkyl phosphinate, wherein the alkyl and alkane groups (^(:6, - where X represents carbon, nitrogen, oxygen, sulfur) And selenium or hydrazine wherein m is self-enthalpy to wherein η has an average value from 1 to about 5, and wherein (Ila) or (lib) each comprises at least one divalent sulfur atom. 46. The method of claim 31, Wherein the electroplating bath further comprises a mixture comprising one or a mixture of two or more of the following formula (Ilia) and/or (Illb) having 119773.doc 200806816; The divalent sulfur sources: R4N^Sk/R5 T and/or ("丨l(Illb) where, in (Ilia) and (Illb), R3, r4, heart and heart may be the same or φ different and independently include hydrogen, halogen, amine , cyano, nitro, nitroso, azo, alkylcarbonyl, decyl, alkoxycarbonyl, aminocarbonyl, alkylamino, dialkylamino, cyclyl, acid , sulphate, phosphonate, phosphinate, sulfoxide, urethane, polyethoxylated alkyl, polypropoxylated alkyl, trans-base, halogen-substituted yard, burned An oxy group, a sulfuric acid alkyl ester, a sulfur-burning group, a pyrenyl group, a alkyl sulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group are (:1-(:6, • where X represents carbon, nitrogen, sulfur, selenium or tellurium and wherein m is from 0 to about 3, where η has an average value from 1 to about 5, and wherein (Ilia) or Each of mb) includes at least one divalent sulfur atom. The method of claim 31, wherein the crystalline chromium deposit does not form a large crack when heated to a temperature of up to about 300 ° C. to An electrodeposition bath for depositing a crystalline chromium deposit, comprising: a source of trivalent chromium having a concentration of at least 仏丨mol and substantially free of additional hexavalent chromium; 119773.doc 200806816 organic additive; source of divalent sulfur; a pH from 4 to about 6.5; an operating temperature of from about 35 ° C to about 95 ° C; and a source of electrical energy applied between the anode and the cathode immersed in the electrodeposition bath. ' 49 · as claimed in claim 48 An electrodeposition bath, wherein the source of divalent sulfur comprises one or a mixture of two or more of the following formula (I): ® X1-R1-(S)n-R2-X2 (I) wherein In (I), X1 and X2 may be the same or different and χΐ and χ2 each independently include hydrogen, halogen, amine group, cyano group, nitro group, nitroso group, azo group, alkyl group, methyl group, and oxygen-burning group. Carbonyl, aminocarbonyl, alkylaminowei, dialkylamino, weigen, sulphate, sulphate, phosphonate, phosphinate, sulfoxide, urethane, poly Oxylated alkyl group, polypropoxylated alkyl group, trans group, halogen-substituted alkyl group, calcined oxygen group, alkyl sulfate, alkane a thio group, an alkylsulfinyl group, an alkylsulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group are €^-(:6, or X1 The bond may be formed from R1 to R2 together with X2, wherein ^^ and 2 may be the same or different and R1 and R2 each independently include a single bond, an alkyl group, an allyl group, an alkenyl group, an alkynyl group, a cyclohexyl group, An aromatic and heteroaromatic ring, a pyrocarbonyl group, an amine carbonyl group, an alkylaminocarbonyl group, a dialkylamino group, a polyethoxylated group, and a polypropoxylated alkyl group, wherein the alkyl groups are Line (VC6, and wherein η has an average value from 1 to about 5. The electrodeposition bath of claim 48, wherein the divalent sulfur source comprises one or more of the compounds of the following formula (Ila) and/or (lib) or both mixture: And r6 (Ha) Wherein (Ila) and (lib), R3, r4, sense 5 and r6 may be the same or different and independently include hydrogen, halogen, amine, cyano, nitro, nitroso, azo, alkane Carbonyl, fluorenyl, alkoxycarbonyl, aminocarbonyl, alkylamino Daidyl, dialkylaminocarboxy, thiol, citrate, sulfinate, phosphonate, phosphinate, hydrazine 1, amine Ruthenium ester group, polyethoxylated alkyl group, polypropoxylated alkyl group, hydroxyl group, functional group substituted by a hydroxyl group, alkoxy group, alkyl sulfate, alkylthio group, alkylsulfinyl group An alkyl sulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group 匕-匕, wherein X represents carbon, nitrogen, milk, sulfur, or silli Or a monument and wherein the melon is self-twisted to about 3, wherein η has an average value from 1 to about 5, and wherein (Ila) or (lib) each comprise at least one divalent sulfur atom. 5. The electrodeposition bath of claim 48, wherein the source of divalent sulfur comprises one or a mixture of two or more of the following compounds of the formula (Ilia) and/or (Illb): 119773.doc 11 200806816 (Ilia) (Hlb) wherein, in (Ilia) and (Illb), R3, R4, R5 and R6 may be the same or different and independently include hydrogen, _, amine, cyano, nitro, succinyl, or Nitrogen, alkylcarbonyl, fluorenyl/alkoxycarbonyl, aminocarbonyl, alkylamino, dialkylamino, sulfhydryl, sulphate, sulphate, phosphonate, phosphinate a sulfoxide, a urethane group, a polyethoxylated alkyl group, a polypropoxylated alkyl group, a carboxylic acid group, an alkoxy group, an alkyl sulfate group, an alkylthio group, An alkylsulfinyl group, a alkylsulfonyl group, an alkyl phosphonate group or an alkyl phosphinate group, wherein the alkyl group and the alkoxy group are ruthenium-iridium, wherein X represents carbon, nitrogen, sulfur And hexose or hydrazine wherein πι is from 0 to about 3, wherein η has an average value from 1 to about 5, and wherein (Ilia) or (Illb) each includes at least one divalent sulfur atom. 52. The electrodeposition bath of claim 48, wherein the source of electrical energy is capable of providing a current density of at least 1 A/dm2 based on the area of the substrate to be plated. 53. The electrodeposition bath of claim 48, wherein when in operation, the bath system deposits a functional chromium deposit that is crystalline when deposited. 54. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit has a lattice parameter of 2.8895 + Μ)·0025 angstroms. 55. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit has a preferred orientation. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit further comprises carbon, nitrogen and sulfur in the chromium deposit. 57. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit comprises from about 1 weight to about 10 weight percent sulfur. The electrodeposition of the substrate 5 is as described in μ, wherein the crystal collateral deposit comprises from about 1% by weight to about 5% by weight of nitrogen. 59. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit comprises carbon in an amount less than the amount that causes the chromium deposit to become amorphous. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit comprises from about 17% by weight to about 4% by weight of sulphur, from about 3% by weight to about 3% by weight of nitrogen and about ο. 1% by weight to about ί% by weight of carbon. 61. The electrodeposition bath of claim 53, wherein the crystalline chromium deposit is substantially free of large cracks. 62. The electrodeposition bath of claim 53, wherein the source of electrical energy is capable of applying one or more of a direct current, a pulsating waveform, or a pulsating periodic inverse waveform. 63. The electrodeposition bath of claim 53, further comprising a source of gas. Two: the project! Crystallized chromium deposits' where the decorative chromium deposits are deposited. A Μ: The object of item W, wherein the deposit is functional or decorative chrome, the method wherein the method deposits a functional or decorative method, wherein the organic additive comprises an amino acid or a thiocyanate or And a dec. a base amine, an amino acid, a hydroxylamine or a polyhydric hydroxyalkanolamine, wherein the alkyl group in the nitrogen source comprises a CrC6 alkyl group. 69. The method of claim 13, which further comprises a source of nitrogen. 70. The method of claim 69, wherein the source of nitrogen comprises ammonium hydroxide or a salt thereof, wherein the alkyl group is a CpC6 alkyl primary, secondary or tertiary alkylamine, An amino acid, a hydroxylamine or a polyhydric hydroxy alkanolamine, wherein the alkyl group in the nitrogen source comprises a Ci_C6 alkyl group. 71. The method of claim 13, wherein the bath comprises selenium or tellurium or a mixture of the two in place of divalent sulfur, or selenium or tellurium or a mixture of the two in addition to divalent sulfur. The method of claim 44, wherein the bath comprises selenium or bismuth in place of divalent sulfur or />:&&> or in addition to monovalent sulfur, a code or hydrazine or a mixture of the two. 73. The method of claim 45, wherein the bath comprises a mixture of divalent sulfur or bismuth or both, or a mixture of both or a mixture of the two. The method of claim 46, wherein the bath comprises a field or a mixture of the two in place of the divalent sulfur' or includes a code or a monument in addition to the divalent euro or a code including a sulfur equivalent to the divalent sulfur. Or 75. The electrodeposition bath of claim 48, wherein the bath is either a mixture of the two or a mixture of the two, or a mixture of the two. 119773.doc • 14·